Treatment of drying oils



I Patented Aug. 9, 1949 TREATMENT OF DRYING OILS Henry G. Berger, Glen Rock, and George S. Crandall and John F. Socolofsky, Woodbury, N. 1., assignors to Socony-Vacnum Oil Company, Incorporated, a corporation of New York No' Drawing. Application'January 13, 1945,

Serial No. 572,744

(claims. (Cl. 260-407) 1 I This invention relates to a process for conversion of drying oils to bodied or polymerized products suitable for preparation of liquid coating compositions such as varnishes and the like.

It has been common practice in the art for I many years to body drying oils, such as tung oil and perilla oil, by cooking at 400 F. to 600 F. for a sufficient period of time. This cooking may be conducted before or after addition of resins such as ester gum. The less active drying oils require extended heating time for completion of such treatment. Excessively long heating times or excessively high cooking temperatures tend to have substantial deleterious effects on the dry properties of the treated oil and may result in gelation. Unduly long drying periods and inferior films are normally found in products from bodyingof the less active drying oils. The

' high-grade drying oils, such as tung and perilla oils, may be cooked to the desired body'without seriously affecting their value as film-forming agents. However, even the better oils are affected by excessive heat treatment.

According to our present process, drying oils are bodied catalytically by treatment in the presence of a polymerization catalyst to produce bodied oils suitable for the preparation of liquid coating compositions. It is known that a variety of polymerization catalysts will effect polymerization of drying oils, and such processes have'been proposed for the manufacture of compositions to be used as lubricants. These prior processes involve catalytic polymerization followed by removal of the catalyst when the desired stage of polymerization has been reached. The products so produced are not suitable for use in varnishes and other liquid coating compositions since the films, if any, formed therefrom are not resistant to frosting and have other disadvantages.

Processes for the production of valuable catalytically bodied oils are described in Patent Number 2,316,187, issued April 13, 1943, to Malcolm F. Pratt and Henry G. Berger. It is there disclosed that if the catalytic bodying reaction is carried'cut at temperatures of about 300 F. or above, bodied oils of suitable properties are obtained. We have now discovered that catalytic bodying may be satisfactorily conducted at lower temperatures, good results being obtained at room temperature, if the reaction is conducted in the manner described below.

The present invention is based on the discovery that satisfactory varnishes can be made from drying oils catalytically bodied at temperatures below 300 F. if a sufficient degree of bodying is attained and the action of the' catalyst is then arrested, whereupon the oil may be blended with resins, thinned and driers and the like added.

In general, a body of at least Z-6 (Gardner-Holdt scale) should be attained before arresting the action of the catalyst. That is, for most purposes, the oil should be catalytically bodied to a stage between Z-6 and gelation by. catalytic action. If the treated oil has a body substantially below Z-6 when catalytic bodying is arrested, there is a strong possibility that films formed therefrom will become frosted. The said. prior patent of Pratt and Berger described varnishes prepared from drying oils bodied catalytically at temperatures below 300 F. and pointed out that these varnishes formed frosted films. The experimental work of the present inventors provides an explanation of this finding and provides a means by which the noted disadvantages may be overcome. Oils bodied catalytically at, the lower temperatures (below 300 F'.) may not be reacted to a sufilcient extent to provide the desired body because additional bodying accompanies the necessary heating to dissolve the resin.

Varnishes can be made from oils bodied to not more than Z-5 (Gardner-Holdt scale) by low temperature catalysis. If a greater body is achieved by catalytic means, gelation occursduring heating to dissolve the resin unless steps described herein are taken. But oils bodied to 2-5 catalytically form varnishes that give frosted films.

According to this invention an inactivator for the catalyst is added when a drying oil containing 'a polymerization catalyst has achieved the desired body. This gelation inhibitor makes it possible to use oils bodied to an extent suflicient that the varnishes prepared therefrom will form hard, lustrous, transparent films; i. e. substantially greater than Z-5. Thus, an oil may be allowed to body catalytically until it has reached a body of more than Z-6+ or until gelation is imminent before addition of inhibitor and subsequent blending with resin. By this procedure varnishes of body A to K at non-volatile have been produced and after addition of the conventional driers, the resultant films dried clear and hard.

In practicing the invention, we use any of the known polymerization catalysts suitable for the purpose from the standpoint of converting the oil to the desired body in a reasonable time when present in concentrations which will not adversely affect films formed therefrom. This is a practical limitation on the process from a commercial standpoint, but it will be apparent to those skilled in the art that relatively less active catalysts may be used where their presence in large quantities will not render the films unfit for the intended purpose ,or where extremely long polymerization periods are not of major importance. Recogniz- 3 ing that the relative activity of the catalyst may be compensated by concentration thereof, the process involves four mutually dependent variables, namely; time, temperature, relative reac-. tivity of the drying oil and catalyst concentration (including catalyst activity).

Obviously, any process within the scope of the invention must involve adjustment of the several variables and critical or optimum conditions generally applicable are impossible to formulate. In general, we prefer to use the more active poly- ,merization catalysts, for example, those of the Friedel-Crafts type of metal halides, with particular preference for-boron fluoride; although many other catalysts, such as hydrogen fluoride,

titanium tetrachloride and other well-known polymerization catalysts may be used to advantage.

The'inactivators or inhibitors are of a varied nature. Nitrogenous basesare particularly valuable for the purpose of inactivating the catalyst and are advantageously used in amounts on the order of 0.2 per cent to one per cent, based on the weight of theoil being treated. Ammonia, pyridine, triamylamine, aniline, and other amines,

.both aromatic and aliphatic, are employed with advantage in inhibiting the catalytic action. Much research has been conducted on catalysis of polymerization reactions in general and many agents are known which have the effect of rendering polymerizationcatalysts inactive. The theory has been proposed that the, inactivators are compounds having a greater tendency to form-addition compounds with the catalyst than does the material being polymerized. The choice of a particular inactivator must be determined by a numberof factors including nature and concentration of catalyst and use to be made of the bodied oil. The driers normally employed in varnishes are also good inactivators but these are preferably used only where resin is dissolved in the oil before bodylng.

Our process may be exemplified by the catalytic bodying of oiticica oil and of an oiticica oil-ester gum varnish base with boron fluoride at room temperature.

- The oil is'uniformly mixed with the catalyst under non-gelling conditions. The catalyzed oil is collected in storage containers and allowed to stand at atmospheric temperatures until the desired degree of polymerization is attained. No agitation nor dilution of the reaction materials is required. The time required for the oil to attain the desired body is naturally dependent upon the activity of the oil being treated, the concentration of the catalyst and the temperature of storage. For illustrative purposes, the following table gives the times required for raw oiticica oil catalyzed with various quantities of boron fluo- .ride to attain a body of Z-5 on Gardner Holdt scale (=98.5 poises) and to reach gel stage when stored at atmospheric temperature.

Concentration Time to reach Time to gel, BF, Per cent 2-5, days days Thus, the concentration of catalyst may be so 75 4 chosenthatthebodyingtimeisoompatiblewith other operating conditions. Although concentrations as low as 0.05% require a reaction time which might not be excessive under some conditions, the more practical range of concentrations appear to be from 0.075% to 0.2% for this oil at room temperature.

when the desired degree of polymerization has been attained as may be determined by periodic test of the body of the reaction mixture, the reaction is stopped. Instead of resorting to the more drastic and complex procedures of dilution and extraction as practiced in the polymerization of oils for lubrication purposes, we stop the catalytic action by the addition of smallquantities of inactivators. Examples of effective inactivators are ammonia, pyridine (0.3%), aniline (0.4%) and amines; A

when applied to the catalytic bodylnl of varnish base, the resin and oil are blended with Just suflicient heating to attain a homogeneom mixture (top temperature approximately 300' 1".) and then subjected to the same type of treatment asused for the treatment of the'drying oil.

Theproducts obtained by this process may be used as bodied oils in the manufacture of varnishes. Theymay be used as prepared or, after the addition of inactivator, they may be stored and utilized as desired.

Our process is superior to the prior art in that it is easily controlled; the concentration of catalyst used is not critical and may be varied over rather wide ranges; no diluent is required and no complicated after-treatment is required.

The present application is a continuation-inpart of our co-pending application, Serial Number 445,970, flied June 5, 1942, now U. 8. Patent No. 2,380,394, issued July 31, 1945.

Example I Raw oiticica oil 99.82 parts and boron fluoride 0.18 parts were thoroughly mixed in a mixing unit of the type described in Patent Number 2,238,864, having a suitable injection valve. The catalvzedoilwasplacedinaclosedcontainer and stored at prevailing room temperature (max. 92 F., min. 62 F.) and the body of the oil determined at frequent intervals with a Gardner- Holdt viscometer. The body of the oil immediately after preparation was Y (=17.6 poises), after 8 hours Z-3 (=46.3 poises), after 14 hours Z-4 (=83.4 poises), after 25 hours Z-5 (=98.5

poises), after 37 hours 2-8, and after 45.5 hours gelation took place.

Example 11 which ranged from a minimum of 69 1". to a maximum of 101 F. This oil attained a body of 2-5 (=98,5 poises) in 5 days and a body of Z-6 (=148 B01888) in 8 1878.

Example III A varnish base consisting of 33.3 parts of ester gum and 66.6 parts of raw oiticica oil was heated for 15 minutes from 74 1".to 267 1''. to completely dissolve the ester gum. This mixture of resin and oil was then mixed'uniformly with 0.1 part of boron fluoride in the mixing equipment referred to in Example 1. After storage ior 7 days, a sample of the product was thinned with petroleum thinner and suitable driers added (0.705% Pb, 0.051% Mn, and 0.009% Co, based on oil content).

shown by the following characteristics:

Body at non-volatile C- (Gardner-Holdt Example IV To oiticica oil containing 0.1% boron fluoride was added 0.3% pyridine at body Z-1 (=27.0 poises) After 134 days storage, the body of this sample was still Z-1. A sample of the same catalyzed 011 without addition of an inactivator gelled in 3 days.

Example V To oiticica oil containing 0.1% boron fluoride was added 0.4% aniline at body Z-1 (=27.0 poises) After 134 days storage, the body of this sample was still Z-1. A sample or the same catalyzed oil without addition of an inactivator gelled in 3 days. v

Example VI Raw oiticica oil 99.92 parts and boron fluoride 0.08 parts were thoroughly mixed as described in Example I. The oil was stored at room temperature until a body of Z-6 was obtained at which time 0.3% triamylamine was added. A 25-gallon varnish was then made from this catalytically bodied oil by dissolving one part ester gum in two parts 011. After thinning to non-volatile with petroleum thinner and adding 0.75% Pb, 0.05% Mn, 0.075% Co (based on oil content) the resultant varnish had a body of J and dried dust free in 1 hour, tack free in 1% hours and hard over night. The dried film was clear and hard.

We claim:

1. The process which comprises polymerizing a drying 011 containing a minor proportion not -'in excess of about 0.2 per cent by weight of a polymerization catalyst of the Friedel-Crafts type at a temperature not substantially above about 300 F. to a body not substantiall lower A varnish having very desirable properties was obtained in this way as therein, by the addition thereto or a small quantity of an aromatic monocyclic amine.

2. The-process which comprises polymerizing a drying oil containing a minor proportion not -in excess of about 0.2 per cent by weight of a polymerization catalyst or the Friedel-Crafts type at a temperature not substantially above about 300 F. to a body not substantially lower than 2-6 (Gardner-Holdt scale), arresting polymerization of said oil before completion of the reaction to gelation, while retaining said catalyst therein, by the addition thereto of a small quantity of pyridine.

3. The process which comprises polymerizing a drying oil containing a minor proportion not in excess of about 0.2 per cent by weight of a polymerization catalyst of the Friedel-Craits type at a temperature not substantially aboveabout 300 F. to a body not substantially lower than Z-6 (Gardner-Holdt scale), arresting polymerization of said oil before completion of the reaction to gelation, while retaining said catalyst therein, by the addition thereto of a small quantity of aniline.

4. The process which comprises polymerizing oiticica oil containing about 0.08 per cent boron fluoride at a temperature not substantially above about 300 F. to a body not substantially lower than Z-6 (Gardner-Hcldt scale), arresting polymerization of said .011 before completion of the reaction to gelation, while retaining said boron fluoride therein, by the addition thereto of about 0.3 per cent oi. pyridine, said percentages bein based on the weight of the oil being treated.

HENRY G. BERGER. GEORGE S. CRANDALL. JOHN F. SOCOLOFSKY.

REFERENCES CITED The following references are of record in the than Z-6 (Gardner-Holdt scale), arresting polymerization or said 011 before completion of the reaction to gelaticn, while retaining said catalyst file or this patent:

UNITED STATES PATENTS Number Name Date 1,924,524 Stoddard Aug. 29, 1933 1,982,707 Thomas Dec. 4, 1934 2,246,007 Robinson June 1'7, 1941 2,316,187 Pratt Apr. 13, 1943 2,324,432 Schantz July 13, 1943 2,360,632 Mann, Jr., et al. Oct. 17, 1944 2,376,088 Robinson May 15, 1945 FOREIGN PATENTS Number Country Date 501,670 Great Britain 1939 

